Determination of hexavalent Cr in river sediments by speciated isotope dilution inductively coupled plasma mass spectrometry

Abstract

During a sampling campaign in September 2015, elevated chromium (Cr) concentrations were observed in sediments of industrially exposed sites of the Sava River (stainless steel production and impact of metallurgic industry). To verify if sediments also contained hazardous hexavalent Cr (Cr(VI)), there was a need to develop a sensitive and reliable analytical procedure for its determination. In the determination of Cr(VI) in environmental samples, it is necessary to evaluate the suitability of the applied analytical methodology for each individual sample matrix. In these studies, the use of isotopically enriched Cr tracers importantly contribute to the validity of the obtained results. In the present work, an analytical procedure was optimised for the extraction of total Cr(VI) from sediments and the content of Cr(VI) determined by high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). To leach the total amount of Cr(VI) from sediments, an ultrasound-assisted extraction procedure was applied at 80 °C, using 2% NaOH + 3% Na₂CO₃ as the extraction solution. The addition of 0.4 mol L^-1 MgCl₂ prevented oxidation of Cr(III) during the extraction step. To control for species interconversion and for an accurate calculation of Cr(VI) concentration by speciated isotope dilution (ID)-ICP-MS, the alkaline extract was doubly spiked with enriched ⁵⁰Cr(VI) and ⁵³Cr(III). The accuracy of the determination of Cr(VI) was verified by analysing the certified reference material CRM 041 (Cr(VI) in soil), and by spike recovery test. Low limits of detection (LOD) and quantification (LOQ) (1.25 and 4.0 μg Cr(VI) kg^-1, respectively) and good repeatability of measurement (relative standard deviation better than ±4.8%) were obtained. The analytical data revealed that Cr(VI) concentrations in sediments of the Sava River did not represent any known environmental hazard.

Keywords: Alkaline extraction; Cr(VI); Sediments; Speciated isotope dilution inductively coupled plasma mass spectrometry; The Sava River.